Herein, laser-induced breakdown spectroscopy (LIBS) is proposed as an effective strategy for selecting appropriate refractories for recovering valuable metals from spent lithium-ion batteries by determining lithium distributions and identifying mineral phases in refractories. The lithium distributions were obtained by measuring lithium emission line intensities at 610.4 nm under 1000-Pa argon in alumina (Al2O3) and magnesia (MgO) crucibles as refractory models used for recovering cobalt from a model lithium-ion battery containing LiCoO2 and graphite by heating crucibles at 1500 °C in argon atmosphere. The lithium distribution showed the presence of LiAlO2 and unreacted LiCoO2 on the Al2O3 crucible, which was protected from undergoing further damage by LiAlO2. The lithium distribution in the MgO crucible indicated that lithium diffused into the MgO crucible, inducing cracking. Therefore, the experiments with LIBS identified the Al2O3-based refractory as suitable for recovering valuable metals from spent lithium-ion batteries, thus providing an effective strategy for selecting appropriate refractories.